The influence of synthetic conditions in the composition and properties of chemically precipitated hydroxyapatite (HAp), fluorine-substituted HAp (xF-HAp) and fluorapatite (FAp) have been examined considering different atmospheres (nitrogen, air and carbon dioxide), temperatures (37 °C and 150 °C) and pressures (hydrothermal conditions). Results indicate that the synthetic conditions not only affect the fluorination degree but also have a pronounced effect on the carbonation degree, the crystallinity, the surface wettability and the thermal stability. Besides, the electrical polarization of HAp-based minerals mainly depends on the fluoride content, the formation of ordered channels of vacancies along the sintering and thermal polarization processes becoming more difficult with increasing fluorination degree. This limits the utilization of xF-HAp and FAp as electro-responsive scaffolds and electrocatalysts, as has been recently proposed for polarized HAp. Finally, the effects of the carbonation and the fluoridation degrees, the concentration fluoride anions supplied from an external source, and the pH on the solubility of HAp-based minerals have been examined. Observations indicate that, although strategies based on the substitution of HAp by xF-HAp or FAp have been proposed for coatings of dental implants, external fluoride anions inhibit the solubility more effectively than the fluorination of the own mineral matrix. Accordingly, HAp combined with an effective external supply of fluoride anions is more appropriated than xF-HAp and FAp for the fabrication of dental coatings.